Hair dyeing compositions comprising 2-(amino or substituted amino)-3-5-substituted phenol compounds and use thereof

ABSTRACT

The present invention relates to compositions for the oxidative dyeing of keratin fibres, comprising a medium suitable for dyeing and a compound 2-(amino or substituted amino)-3,5-substituted phenol compounds according to the Formula (I), as defined herein.

FIELD OF THE INVENTION

The present invention relates to compositions for the oxidative dyeingof keratin fibres (preferably hair) comprising 2-(amino or substitutedamino)-3,5-substituted phenol compounds, and the use thereof.

BACKGROUND OF THE INVENTION

Dyeing of keratin fibres, particularly hair, is known. The desire toalter the colours of hair is not a facet of modern times. Hair colour isaltered to accommodate changes in fashion, style, and personalpreference. However, obtaining good colouring and wearability withoutundesirable side effects to the hair and skin, remains an elusive goal.

A suitable method of colouring hair is through oxidative dyeing. Avariety of colours may be obtained, including yellows. Although theinventors choose not to speculate on the veracity of the adage accordingto which reputedly “blondes have more fin,” they do recognize thatyellow dyes themselves are desired.

Yellow dyes, particularly those used in colouring hair, should providegood colouring, including intensity of colouration and/or fastness, andbe able to perform in spite of external agents, such as light,particularly sunlight, adverse weather conditions, washing and styling,permanent waving, perspiration, and/or friction. Such dyes should alsobe favourable as to toxicology and dermatology. They should be useful inproviding a wide range of shades when combined with other ingredientsand process stages, too.

The use of 2-aminophenol (also known as ortho-aminophenol or OAP) andsome derivatives thereof, for yellow dyeing of keratin is known. Forexample, U.S. Pat. No. 4,396,392 (Wella, AG) discloses2-amino-5-methyl-phenol, WO 02/058,657 (Clairol, Inc.) discloses2-(amino or amino substituted)-5-methyl-phenol, and DE 202,06,274U1(Wella, AG) discloses 2,3-diaminophenol derivatives, each for use inproviding yellow colours, alone and in combination with other colouringagents. However, many previous oxidative dye compounds and combinationsof such compounds resulting in yellow colourations have demonstratedpoor wearability and stability to light, and some have recentlyexperienced objections to their use from a toxicological standpoint.OAP, in particular, has been found to provide poor yellow, e.g. withoff-tones. One alternative approach has been to use direct non-oxidativedyes alone or in combination with lessened quantities of oxidative dyes.However, this approach has been found to result in poor wash fastnessupon shampooing, among other undesirable effects. Thus, there remains aneed to provide further oxidative dye alternatives to known dyes,preferably yellow dyes, and compositions for dyeing of hair comprisingthem, that produce good colouration, preferably a bright yellowcolouration, that exhibit good dye uptake by the hair, are useful inproviding shades or colours which are stable over a reasonable period oftime, provide good wash fastness and wearability, good selectivity, donot undergo significant change on exposure to light, shampooing or acidperspiration, and/or exhibit a favourable safety profile.

EP 848942 describes substituted anilines and phenols in hair colourantapplications. DE 3440263 describes copper complexes which are preparedfrom starting materials and intermediates including -2-aminophenol 3,5disulphonic acid.

It has now been surprisingly found that by placing substituents in the 3and 5 position of 2-(amino and substituted amino) phenols compoundsexhibiting one or more of the aforementioned desirable qualities may beprovided. Without being bound by theory, it is believed that theaddition of such substituents in these positions may provide similarimproved yellow colour formation and wash fastness with improvedtoxicology via steric hinderance of the active groups (—OH, NH₂) versusprevious 2-amino phenols and 2-amino phenol derivatives.

SUMMARY OF THE INVENTION

This invention relates to a composition for the oxidative dyeing ofkeratin fibres, comprising a medium suitable for dyeing comprising and acompound 2-(amino or substituted amino)-3,5-substituted phenol accordingto the Formula (I), as defined herein. This invention further relates toa method for oxidative dyeing of keratin fibres, comprising applyingsuch compositions in the presence of an oxidizing agent, for a periodsufficient to develop the desired colouration.

DETAILED DESCRIPTION OF THE INVENTION

Except as otherwise noted, amounts represent approximate weight percentof the actual amount of the ingredient, and do not include solvents,fillers or other materials which may be combined with the ingredient incommercially available products, and the amounts include the compositionin the form of intended use. Except as otherwise noted, all amountsincluding part, percentages, and proportions are understood to bemodified by the word “about”, and amounts are not intended to indicatesignificant digits.

As used herein, the term “hair” refers to keratinous fibres on a living,e.g. a person, or non-living body, e.g. in a wig, hairpiece, or otheraggregation of non-living keratinous fibres. Mammalian, preferablyhuman, hair is a preferred. Notably, hair, wool, fur, and otherkeratinous fibres are suitable substrates for colouring by the compoundsand compositions described herein.

As used herein, the term “hair dyeing composition” refers to thecomposition containing one or more oxidation dyes, including thecompounds described herein, prior to admixture with the developercomposition. The term “developer composition” (which encompasses theterm oxidizing agent composition) refers to compositions containing anoxidizing agent prior to admixture with the hair dyeing composition. Theterm “hair dyeing system” refers to the combination of the hair dyeingcomposition and the developer composition before admixture, and mayfurther include a conditioner product and instructions, such product orsystem often being provided packaged as a kit. The term “hair dyeingproduct composition” refers to the composition formed by mixing the hairdyeing composition and the developer composition.

As used herein, “heteroalkyl” means a paraffinic (paraffin is alsocalled alkane) hydrocarbon group containing at least one heteroatom(element other than carbon).

As used herein, “heteroaliphatic” means a group of organic compoundscharacterised by straight- or branched-chain arrangement of theconstituent carbon comprising at least one heteroatom. Heteroaliphaticsare comprised of three sub-groups: heteroalkanes, all of which aresaturated; heteroalkenes, which are unsaturated; and heteroalkynes,which contain a triple bond. In complex structures the chains may bebranched or cross-linked.

As used herein, “heteroolefinic” means a class of unsaturatedhydrocarbons containing at least one heteroatom and having one of moredouble bonds. Those containing one double bond are called heteroalkenes,and those with two heteroalkadienes, or heterodiolefin. They are namedafter their corresponding paraffins by adding ‘-ene’ or ‘-ylene’ to thestem.

As used herein, “cosmetically acceptable” means that ingredients whichthe term describes are suitable for use in contact with the skin or hairof humans and lower animals without undue toxicity, incompatibility,instability, irritation, allergic response, and the like.

I. Composition Components

The present invention relates to compositions for the oxidative dyeingof keratin fibres comprise a medium suitable for dyeing and a compoundof the Formula (I), or its salts with an inorganic or organic acid. Suchcompounds will typically be present in an amount ranging from 0.001% to10%, preferably from 0.01% to 5%, by weight, of the hair dyecomposition.

According to the present invention the compounds of the Formula (I), orits salts with an inorganic or organic acid is defined below:

wherein both of R³ and R⁵ are substituted and are independently selectedfrom:

-   -   (a) the group of C-linked monovalent substituents consisting        of: (i) substituted or unsubstituted, straight or branched,        alkyl, mono- or poly-unsaturated alkyl, heteroalkyl, aliphatic,        heteroaliphatic, or heteroolefinic systems, (ii) substituted or        unsubstituted, mono- or poly-cyclic aliphatic, aryl, or        heterocyclic systems, or (iii) substituted or unsubstituted,        mono-, poly-, or per-fluoro alkyl systems; said systems of        (i), (ii) and (iii) independently comprising from 1 to 10 carbon        atoms and 0 to 5 heteroatoms independently selected from O, S,        N, P, and Si;    -   (b) the group of S-linked monovalent substituents consisting of        SA¹, SCN, SSA¹, SOA₁, SO₂NA¹A², SNA¹A², and SONA¹A²;    -   (c) the group of O-linked monovalent substituents consisting of        OA⁴, OCN and ONA¹A²;    -   (d) the group of N-linked monovalent substituents consisting of        NA¹A⁵, (NA¹A²A³)⁺, NC, NA¹OA², NA¹SA², NCO, NCS, N═NA¹, N═NOA¹,        NA¹CN, NA¹NA²A¹;    -   (e) the group of monovalent substituents consisting of CON₃,        CONA¹ ₂, CONA¹COA², C(═NA¹)NA¹A², CHO, CHS, CN, NC, and X; and    -   (f) the group consisting fluoroalkyl monovalent substituents        consisting of mono-, poly-, or per-fluoro alkyl systems        comprising from 1 to 12 carbon atoms and 0 to 4 heteroatoms.

Preferably R³, and R⁵ are independently selected from:

-   -   (a) the group of C-linked monovalent substituents consisting        of: (i) substituted or unsubstituted, straight or branched,        alkyl, mono- or poly-unsaturated alkyl, heteroalkyl, aliphatic,        heteroaliphatic, or heteroolefinic systems, (ii) substituted or        unsubstituted, mono- or poly-cyclic aliphatic, aryl, or        heterocyclic systems, or (iii) substituted or unsubstituted,        mono-, poly-, or per-fluoro alkyl systems; said systems of        (i), (ii) and (iii) independently comprising from 1 to 10 carbon        atoms and 0 to 5 heteroatoms independently selected from O, S        and N;    -   (e) the group of monovalent substituents consisting of CON₃,        CONA¹ ₂, CONA¹COA², C(═NA¹)NA¹A², CHO, CHS, CN, NC, and X; and    -   (f) the group consisting of fluoroalkyl monovalent substituents        consisting of mono-, poly-, or per-fluoro alkyl systems        comprising from 1 to 8 carbon atoms and 0 to 3 heteroatoms.

More preferably R³, and R⁵ are independently selected from:—

-   -   (a) the group of C-linked monovalent substituents consisting        of: (i) substituted or unsubstituted, straight or branched,        alkyl, mono- or poly-unsaturated alkyl, heteroalkyl, aliphatic,        heteroaliphatic, or heteroolefinic systems, (ii) substituted or        unsubstituted, mono- or poly-cyclic aliphatic, aryl, or        heterocyclic systems, or (iii) substituted or unsubstituted,        mono-, poly-, or per-fluoro alkyl systems; said systems of        (i), (ii) and (iii) independently comprising from 1 to 6 carbon        atoms and 0 to 2 heteroatoms independently selected from O, S        and N.

Most preferably R³ and R⁵ are independently selected from:—

-   -   (a) the group of C-linked monovalent substituents consisting        of: (i) substituted or unsubstituted, straight or branched,        alkyl, mono- or poly-unsaturated alkyl, heteroalkyl, aliphatic,        heteroaliphatic, or heteroolefinic systems comprising from 1 to        6 carbon atoms and 0 to 2 heteroatoms selected from O, S and N.

For the groups (b) to (e), described herein above, A¹, A², and A³ aremonovalent and are independently selected from:

-   -   (1) H,    -   (2) substituted or unsubstituted, straight or branched, alkyl,        mono- or poly-unsaturated alkyl, heteroalkyl, aliphatic,        heteroaliphatic, or heteroolefinic systems,    -   (3) substituted or unsubstituted, mono- or poly-cyclic        aliphatic, aryl, or heterocyclic systems, or    -   (4) substituted or unsubstituted, mono-, poly-, or per-fluoro        alkyl systems;    -   said systems of (2), (3) and (4) comprising from 1 to 10 carbon        atoms and 0 to 5 heteroatoms selected from O, S, N, P, and Si;        and wherein X is a halogen selected from the group consisting of        F, Cl, Br, and I,    -   A⁴ is monovalent and is independently selected from:    -   (1) substituted or unsubstituted, straight or branched, alkyl,        mono- or poly-unsaturated alkyl, heteroalkyl, aliphatic,        heteroaliphatic, or heteroolefinic systems,    -   (2) substituted or unsubstituted, mono- or poly-cyclic        aliphatic, aryl, or heterocyclic systems, or    -   (3) substituted or unsubstituted, mono-, poly-, or per-fluoro        alkyl systems;    -   said systems of (1), (2) and (3) comprising from 2 to 10 carbon        atoms and 0 to 5 heteroatoms selected from O, S, N, P, and Si,    -   A⁵ is monovalent and is independently selected from:    -   (1) substituted or unsubstituted, straight or branched, alkyl,        mono- or poly-unsaturated alkyl, heteroalkyl, aliphatic,        heteroaliphatic, or heteroolefinic systems,    -   (2) substituted or unsubstituted, mono- or poly-cyclic        aliphatic, aryl, or heterocyclic systems, or    -   (3) substituted or unsubstituted, mono-, poly-, or per-fluoro        alkyl systems; said systems of (1), (2) and (3) comprising from        1 to 10 carbon atoms and 0 to 5 heteroatoms selected from O, S,        N, P, and Si; and wherein X is a halogen selected from the group        consisting of F, Cl, Br, and I.

R² is selected from any of the groups defined for R³ and R⁵ herein aboveand H, preferably R² is H.

Particularly preferred compounds of the present invention are listedbelow, wherein R³ and R⁵ are independently selected from methyl, ethyland —CH₂—O—CH₃:

The 3,5-substituted amino phenols of the present invention may bereadily synthesised using routes known in the literature. The mostcommon route to 2-aminophenols is by the nitration of the phenol withdilute aqueous nitric acid, followed by reduction of the readilyseparated 2-nitro isomer to 2-aminophenol. The most common and generalroute to the polysubstituted 2-aminophenols is the same, but startingfrom the appropriately substituted phenol. Thus the 3,5,disubstituted2-aminophenols require the appropriately substituted di-substitutedphenol, as shown;

The R³ and R⁵ groups in each case can be the same or different asdefined herein above.

When R³ and R⁵ groups in the starting 3,5-disubstituted phenol aredifferent, then two aminophenols are possible;

Their formation and product ratio will depend upon the nitration of thephenol which will be governed by the electronic and steric effects of R³and R⁵ in the usual manner.

The following generic classes are readily synthesized in order toproduce the required starting materials.

Moreover, a number of the starting compounds are also commerciallyavailable (e.g. from Aldrich), as listed below, whilst many morecompounds could be readily synthesised using the standard methodsdescribed hereinabove

Alternatively many other compounds may be synthesized from commercial orknown compounds by standard electrophilic aromatic substitution andfunctional group manipulation. For example;

and also;

and the diester;

All with mono-nitration ortho to the OH group at an appropriate stage.Similar standard sequences (mono or di-) are available from otherstarting materials such as;

Whilst the general route to these compounds, described above, is basedon phenols as the starting materials, in particular cases it may be moreattractive to introduce the phenolic group during the synthesis. Themain methods available for this route are summarized below;

For several other routes see ‘Comprehesive Organic Functional GroupTransformations’, Elsevier, Vol. 2 pp. 646-674.

As phenols are electron rich they are very reactive towardselectrophilic substitution, as in the nitration reactions above.Consequently, other standard electrophilic aromatic substitutionreactions, such as halogenation, sulphonation, alkylation and acylationare thus also applicable. Additionally, there is a group of reactionsspecific to phenols which are available for the introduction ofsubstitutents such as those illustrated below;

An alternative route is to utilize the re-arrangement ofN-aryl-hydroxylamines into o-aminophenols (if the p position is blocked)as illustrated below:

ARNHOH can also be formed by careful oxidation of ArNH₂. The potentiallyvaluable aspect of this rearrangement for this synthesis is that theposition para to the NHOH is blocked (hence the usually major isomercannot be formed). This is an advantage over the nitration and reductionof the phenol route.

Given that the OH and NH₂ groups of aminophenols are reactive, it may benecessary in some synthetic sequences to ‘protect’ one or both of themto avoid unwanted chemistry. This is readily done for OH by alkylation(e.g. methylation) and deblocking with acid (HBr), and for NH₂ byacylation (e.g. acetylation) and deblocking with base (aq. NaOH);

Alternatively, both functional groups can be protected at the same timeif necessary by forming them into a cyclic structure, for example;

Finally, in electrophilic substitution of the aromatic ring in a givensynthesis, the most reactive site of substitution may not be the desiredone. In such cases the most reactive site may be sulphonated (with H₂SO₄or SO₃/H₂SO₄) thereby blocking this position. Electrophilic substitutionat the desired site is then followed by deblocking the sulphonic acid byheating with dilute sulphuric acid (since sulphonation is a reversiblereaction). For example (the main product being the para-substitutedcompound due to steric reasons);

However, the ortho-isomer may also be prepared as follows;

Thus, by using the chemistry summarized herein above, it is possible toprepare almost any desired 3,5-substituted 2-aminophenol.Medium

The medium suitable for dyeing may be selected from water, or a mixtureof water and at least one organic solvent to dissolve the compounds thatwould not typically be sufficiently soluble in water. Suitable organicsolvents for use herein include, but are not limited to: C1 to C4 loweralkanols (e.g., ethanol, propanol, isopropanol), aromatic alcohols (e.g.benzyl alcohol and phenoxyethanol); polyols and polyol ethers (e.g.,carbitols, 2-butoxyethanol, propylene glycol, propylene glycolmonomethyl ether, diethylene glycol monoethyl ether, monomethyl ether,hexylene glycol, glycerol, ethoxy glycol), and propylene carbonate. Whenpresent, organic solvents are typically present in an amount rangingfrom 1% to 30%, by weight, of the composition. Preferred solvents arewater, ethanol, propanol, isopropanol, glycerol, 1,2-propylene glycol,hexylene glycol, ethoxy diglycol, and mixtures thereof.

The inventive compositions may, in some embodiments, further compriseadditional optional components known, conventionally used, or otherwiseeffective for use in oxidative dye compositions, including but limitedto: primary intermediate dye compounds; coupler dye compounds; directdyes; anionic, cationic, nonionic, amphoteric or zwitterionicsurfactants, or mixtures thereof; anionic, cationic, nonionic,amphoteric or zwitterionic polymers, or mixtures thereof; inorganic ororganic thickeners; conditioning agents; oxidising agents; alkalisingagents; antioxidants and radical scavengers; penetration agents;chelating and sequestering agents; fragrances; buffers; dispersingagents; peroxide stabilizing agents; natural ingredients, e.g. proteinsand protein derivatives, and plant materials (e.g. aloe, chamomile andhenna extracts); silicones (volatile or non-volatile, modified ornon-modified), film-forming agents, ceramides, preserving agents; andopacifiers.

Some adjuvants referred to above, but not specifically described below,which are suitable are listed in the International Cosmetics IngredientDictionary and Handbook, (8^(th) ed.; The Cosmetics, Toiletry, andFragrance Association). Particularly, vol. 2, sections 3 (ChemicalClasses) and 4 (Functions) are useful in identifying specific adjuvantsto achieve a particular purpose or multipurpose.

Oxidative Dye Compounds

The oxidative dye precursors according to Formula I (above) that arecomprised within the inventive compositions may be present alone asdyeing agents, and can advantageously behave both like an oxidation baseand like a coupler, e.g. self-coupling compounds. They may also be usedin combination with one or more primary intermediates, and/or couplers,and in combination with one or more oxidizing agent. All known couplerand primary intermediate combinations are usable in the inventivecompositions.

The compounds suitable for use in the inventive compositions (includingthose optionally added), in so far as they are bases, may be used asfree bases or in the form of their physiologically compatible salts withorganic or inorganic acids, such as hydrochloric, hydrobromic, citric,acetic, lactic, succinic, tartaric, or sulfuric acids, or, in so far asthey have aromatic OH groups, in the form of their salts with bases,such as alkali phenolates.

Optional couplers, when present, are typically present in an amount suchthat in aggregate the concentration of couplers and the compounds ofFormula (I) in the composition ranges from 0.002% to 10%, preferablyfrom 0.01% to 5%, by weight, of the hair dyeing composition. Optionalprimary intermediates, when present, are present in an effective dyeingconcentration, typically an amount from 0.001% to 10%, preferably from0.01% to 5%, by weight, of the hair dyeing composition. The total amountof dye compounds (e.g., optional primary intermediates, optional couplercompounds, and the compounds of Formula (I)) in the hair dyeingcompositions of this invention will typically range from 0.002% to 20%,preferably from 0.04% to 10%, more preferably from 0.1% to 7%, byweight, of the hair dyeing composition.

Primary Intermediates

Suitable primary intermediates for use in the compositions describedherein include, but are not limited to p-phenylenediamine derivatives,e.g. benzene-1,4-diamine (commonly known as p-phenylenediamine),2-methyl-benzene-1,4-diamine, 2-chloro-benzene-1,4-diamine,N-phenyl-benzene-1,4-diamine, N-(2-ethoxyethyl)benzene-1,4-diamine,2-[(4-amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol, (commonly known asN,N-bis(2-hydroxyethyl)-p-phenylenediamine)(2,5-diamino-phenyl)-methanol, 1-(2′-Hydroxyethyl)-2,5-diaminobenzene,2-(2,5-diamino-phenyl)-ethanol, N-(4-aminophenyl)benzene-1,4-diamine,2,6-dimethyl-benzene-1,4-diamine, 2-isopropyl-benzene-1,4-diamine,1-[(4-aminophenyl)amino]-propan-2-ol, 2-propyl-benzene-1,4-diamine,1,3-bis[(4-aminophenyl)(2-hydroxyethyl)amino]propan-2-ol,N⁴,N⁴,2-trimethylbenzene-1,4-diamine, 2-methoxy-benzene-1,4-diamine,1-(2,5-diaminophenyl)ethane-1,2-diol, 2,3-dimethyl-benzene-1,4-diamine,N-(4-amino-3-hydroxy-phenyl)-acetamide, 2,6-diethylbenzene-1,4-diamine,2,5-dimethylbenzene-1,4-diamine, 2-thien-2-ylbenzene-1,4-diamine,2-thien-3-ylbenzene-1,4-diamine, 2-pyridin-3-ylbenzene-1,4-diamine,1,1′-biphenyl-2,5-diamine, 2-(methoxymethyl)benzene-1,4-diamine,2-(aminomethyl)benzene-1,4-diamine, 2-(2,5-diaminophenoxy)ethanol,N-[2-(2,5-diaminophenoxy)ethyl]-acetamide,N,N-dimethylbenzene-1,4-diamine, N,N-diethylbenzene-1,4-diamine,N,N-dipropylbenzene-1,4-diamine, 2-[(4-aminophenyl)(ethyl)amino]ethanol,2-[(4-amino-3-methyl-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol,N-(2-methoxyethyl)-benzene-1,4-diamine,3-[(4-aminophenyl)amino]propan-1-ol,3-[(4-aminophenyl)-amino]propane-1,2-diol,N-{4-[(4-aminophenyl)amino]butyl}benzene-1,4-diamine, and2-[2-(2-{2-[(2,5-diaminophenyl)-oxy]ethoxy}ethoxy)ethoxy]benzene-1,4-diamine;1,3-Bis(N(2-Hydroxyethyl)-N-(4-amino-phenyl)amino)-2-propanol;2,2′-[1,2-Ethanediyl-bis-(oxy-2,1-ethanediyloxy)]-bis-benzene-1,4-diamine;N,N-Bis(2-hydroxyethyl)-p-phenylinediamine;

-   p-aminophenol derivatives such as: 4-amino-phenol (commonly known as    p-aminophenol), 4-methylamino-phenol, 4-amino-3-methyl-phenol,    4-amino-2-hydroxymethyl-phenol, 4-amino-2-methyl-phenol,    4-amino-1-hydroxy-2-(2′-hydroxyethylaminomethyl)benzene,    4-amino-2-methoxymethyl-phenol, 5-amino-2-hydroxy-benzoic acid,    1-(5-amino-2-hydroxy-phenyl)-ethane-1,2-diol,    4-amino-2-(2-hydroxy-ethyl)-phenol, 4-amino-3-(hydroxymethyl)phenol,    4-amino-3-fluoro-phenol, 4-amino-2-(aminomethyl)-phenol,    4-amino-2-fluoro-phenol; 1-Hydroxy-2,4-diaminobenzene;    1-(2′-Hydroxyethyloxy)-2,4-diaminobenzene;    2,4-Diamino-5-methylphenetol;-   o-phenylenediamine derivatives such as: 3,4-Diaminobenzoic acid and    salts thereof;-   o-aminophenol derivatives such as: 2-amino-phenol (commonly known as    o-aminophenol), 2,4-diaminophenol, 2-amino-5-methyl-phenol,    2-amino-6-methyl-phenol, N-(4-amino-3-hydroxy-phenyl)-acetamide,    2-amino-4-methyl-phenol, 2-amino-5-ethyl-phenol, 2-amino-5-phenyl    phenol and 2-amino-5-methoxy-methylphenol; and-   heterocyclic derivatives such as: pyrimidine-2,4,5,6-tetramine    (commonly known as 2,4,5,6-tetraminopyridine),    1-methyl-1H-pyrazole-4,5-diamine,    2-(4,5-diamino-1H-pyrazol-1-yl)ethanol,    N²,N²-dimethyl-pyridine-2,5-diamine,    2-[(3-amino-6-methoxypyridin-2-yl)amino]ethanol,    6-methoxy-N²-methyl-pyridine-2,3-diamine,    2,5,6-triaminopyrimidin-4(1H)-one, pyridine-2,5-diamine,    1-isopropyl-1H-pyrazole-4,5-diamine,    1-(4-methylbenzyl)-1H-pyrazole-4,5-diamine,    1-(benzyl)-1H-pyrazole-4,5-diamine,    1-(4-chlorobenzyl)-1H-pyrazole-4,5-diamine,    pyrazolo[1,5-a]-pyrimidine-3,7-diamine,    5,6,7-trimethylpyrazolo[1,5-a]pyrimidin-3-ylamine hydrochloride,    7-methylpyrazolo[1,5-a]pyrimidin-3-ylamine hydrochloride,    2,5,6,7-teramethyl-pyrazolo[1,5-a]pyrimidin-3-ylamine hydrochloride,    5,7-di-tert-butylpyrazolo[1,5-a]pyrimidin-3-ylamine hydrochloride,    5,7-di-trifluoromethyl-pyrazolo[1,5-a]pyrimidin-3-ylamine    hydrochloride, 2-methylpyrazolo[1,5-a]pyrimidin-3,7-diamine    hydrochloride; 4-Hydroxy-2,5,6-triaminopyrimidine;    1-(2′hydroxyethyl)-amino-3,4-methylene dioxybenzene; and    1-Hydroxyethyl-4,5-diaminopyrazole sulphate.

Preferred primary intermediates include but are not limited to:p-phenylenediamine derivatives such as: 2-methyl-benzene-1,4-diamine;benzene-1,4-diamine; 1-(2,5-diamino-phenyl)-ethanol;2-(2,5-diamino-phenyl)-ethanol; N-(2-methoxyethyl)benzene-1,4-diamine;2-[(4-amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol;1-(2,5-diaminophenyl)ethane-1,2-diol;1-(2′-Hydroxyethyl)-2,5-diaminobenzene;1,3-Bis(N(2-Hydroxyethyl)-N-(4-amino-phenyl)amino)-2-propanol;2,2′-[1,2-Ethanediyl-bis-(oxy-2,1-ethanediyloxy)]-bis-benzene-1,4-diamine;N,N-Bis(2-hydroxyethyl)-p-phenylinediamine; and mixtures thereof;

-   p-aminophenol derivatives such as: 4-amino-phenol,    4-methylamino-phenol, 4-amino-3-methyl-phenol,    4-amino-2-methoxymethyl-phenol;    1-(5-amino-2-hydroxy-phenyl)-ethane-1,2-diol;    1-Hydroxy-2,4-diaminobenzene;    1-(2′-Hydroxyethyloxy)-2,4-diaminobenzene;    4-Amino-2-aminomethylphenol; 2,4-Diamino-5-methylphenetol;    4-Amino-1-hydroxy-2-(2′-hydroxyethylaminomethyl)benzene;    1-methoxy-2-amino-4-(2′hydroxyethylamino)benzene; 5-aminosalicylic    acid and salts thereof; and mixtures thereof;-   o-phenylenediamine derivatives such as: 3,4-Diaminobenzoic acid and    salts thereof;-   o-aminophenol derivatives such as: 2-amino-phenol (commonly known as    o-aminophenol), 2,4-diaminophenol, 2-amino-5-methyl-phenol,    2-amino-6-methyl-phenol, N-(4-amino-3-hydroxy-phenyl)-acetamide,    2-amino-4-methyl-phenol, 2-amino-5-ethyl-phenol, 2-amino-5-phenyl    phenol and 2-amino-5-methoxymethyl-phenol; and-   heterocyclic derivatives such as: pyrimidine-2,4,5,6-tetramine;    1-methyl-1H-pyrazole-4,5-diamine;    2-(4,5-diamino-1H-pyrazol-1-yl)ethanol;    1-(4-methylbenzyl)-1H-pyrazole-4,5-diamine;    1-(benzyl)-1H-pyrazole-4,5-diamine;    N²,N²-dimethyl-pyridine-2,5-diamine;    4-Hydroxy-2,5,6-triaminopyrimidine;    1-(2′hydroxyethyl)-amino-3,4-methylene dioxybenzene; and    1-Hydroxyethyl-4,5-diaminopyrazole sulphate; and mixtures thereof.

More preferred primary intermediates include:2-methyl-benzene-1,4-diamine; benzene-1,4-diamine;N,N-Bis(2-hydroxyethyl)-p-phenylinediamine; 4-amino-phenol;4-methylamino-phenol; 4-amino-3-methyl-phenol;1-Hydroxy-2,4-diaminobenzene; 2-amino-phenol; 2-amino-5-methyl-phenol;2-amino-6-methyl-phenol; 1-methyl-1H-pyrazole-4,5-diamine;1-Hydroxyethyl-4,5-diaminopyrazole sulphate;2-(4,5-diamino-1H-pyrazol-1-yl)ethanol; and mixtures thereof.

Couplers

Suitable couplers for use in the compositions described herein include,but are not limited to: phenols, resorcinol and naphthol derivativessuch as: naphthalene-1,7-diol, benzene-1,3-diol,4-chlorobenzene-1,3-diol, naphthalen-1-ol, 2-methyl-naphthalen-1-ol,naphthalene-1,5-diol, naphthalene-2,7-diol, benzene-1,4-diol,2-methyl-benzene-1,3-diol, 7-amino-4-hydroxy-naphthalene-2-sulfonicacid, 2-isopropyl-5-methylphenol,1,2,3,4-tetrahydro-naphthalene-1,5-diol, 2-chloro-benzene-1,3-diol,4-hydroxy-naphthalene-1-sulfonic acid, benzene-1,2,3-triol,naphthalene-2,3-diol, 5-dichloro-2-methylbenzene-1,3-diol,4,6-dichlorobenzene-1,3-diol, 2,3-dihydroxy-[1,4]naphthoquinone; and1-Acetoxy-2-methylnaphthalene;

-   m-phenylenediamines such as: 2,4-diaminophenol, benzene-1,3-diamine,    2-(2,4-diamino-phenoxy)-ethanol,    2-[(3-amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol,    2-mehyl-benzene-1,3-diamine,    2-[[2-(2,4-diamino-phenoxy)-ethyl]-(2-hydroxy-ethyl)-amino]-ethanol,    4-{3-[(2,4-diaminophenyl)oxy]propoxy}benzene-1,3-diamine,    2-(2,4-diamino-phenyl)-ethanol,    2-(3-amino-4-methoxy-phenylamino)-ethanol,    4-(2-amino-ethoxy)-benzene-1,3-diamine, (2,4-diamino-phenoxy)-acetic    acid, 2-[2,4-diamino-5-(2-hydroxy-ethoxy)-phenoxy]-ethanol,    4-ethoxy-6-methyl-benzene-1,3-diamine,    2-(2,4-diamino-5-methyl-phenoxy)-ethanol,    4,6-dimethoxy-benzene-1,3-diamine,    2-[3-(2-hydroxy-ethylamino)-2-methyl-phenylamino]-ethanol,    3-(2,4-diamino-phenoxy)-propan-1-ol,    N-[3-(dimethylamino)phenyl]urea,    4-methoxy-6-methylbenzene-1,3-diamine,    4-fluoro-6-methylbenzene-1,3-diamine,    2-({3-[(2-hydroxyethyl)amino]-4,6-dimethoxyphenyl}-amino)ethanol,    3-(2,4-diaminophenoxy)-propane-1,2-diol,    2-[2-amino-4-(methylamino)-phenoxy]ethanol,    2-[(5-amino-2-ethoxy-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol,    2-[(3-aminophenyl)amino]ethanol,    2,4-Diamino-5-(2′-hydroxyethyloxy)toluene;    N,N-Dimethyl-3-ureidoaniline; N-(2-aminoethyl)benzene-1,3-diamine,    4-{[(2,4-diamino-phenyl)oxy]methoxy}-benzene-1,3-diamine,    1-methyl-2,6-bis(2-hydroxyethylamino)benzene; and    2,4-dimethoxybenzene-1,3-diamine;-   m-aminophenols such as: 3-amino-phenol,    2-(3-hydroxy-4-methyl-phenylamino)-acetamide,    2-(3-hydroxy-phenylamino)-acetamide, 5-amino-2-methyl-phenol,    5-(2-hydroxy-ethylamino)-2-methyl-phenol,    5-amino-2,4-dichloro-phenol, 3-amino-2-methyl-phenol,    3-amino-2-chloro-6-methyl-phenol,    5-amino-2-(2-hydroxy-ethoxy)-phenol,    2chloro-5-(2,2,2-trifluoro-ethylamino)-phenol,    5-amino-4-chloro-2-methyl-phenol, 3-cyclopentylamino-phenol,    5-[(2-hydroxyethyl)amino]-4-methoxy-2-methylphenol,    5-amino-4-methoxy-2-methylphenol, 3-(dimethylamino)phenol,    3-(diethylamino)phenol, 5-amino-4-fluoro-2-methylphenol,    5-amino-4-ethoxy-2-methylphenol, 3-amino-2,4-dichloro-phenol,    3-[(2-methoxyethyl)amino]phenol, 3-[(2-hydroxyethyl)amino]phenol,    5-amino-2-ethyl-phenol, 5-amino-2-methoxyphenol,    5-[(3-hydroxy-propyl)amino]-2-methylphenol,    3-[(3-hydroxy-2-methylphenyl)-amino]propane-1,2-diol,    3-[(2-hydroxyethyl)amino]-2-methylphenol;    1-Methyl-2-hydroxy-4-(2′-hydroxyethyl)amino-benzene;    1,3-Bis-(2,4-Diaminophenoxy)propane;    1-Hydroxy-2-methyl-5-amino-6-chlorobenzene; and-   heterocyclic derivatives such as:    3,4-dihydro-2H-1,4-benzoxazin-6-ol,    4-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one,    6-methoxyquinolin-8-amine, 4-methylpyridine-2,6-diol,    2,3-dihydro-1,4-benzodioxin-5-ol, 1,3-benzodioxol-5-ol,    2-(1,3-benzodioxol-5-ylamino)ethanol, 3,4-dimethylpyridine-2,6-diol,    5-chloropyridine-2,3-diol, 2,6-dimethoxypyridine-3,5-diamine,    1,3-benzodioxol-5-amine,    2-{[3,5-diamino-6-(2-hydroxy-ethoxy)-pyridin-2-yl]oxy}-ethanol,    1H-indol-4-ol, 5-amino-2,6-dimethoxypyridin-3-ol,    1H-indole-5,6-diol, 1H-indol-7-ol, 1H-indol-5-ol, 1H-indol-6-ol,    6-bromo-1,3-benzodioxol-5-ol, 2-aminopyridin-3-ol,    pyridine-2,6-diamine,    3-[(3,5-diaminopyridin-2-yl)oxy]propane-1,2-diol,    5-[(3,5-diaminopyridin-2-yl)oxy]pentane-1,3-diol,    1H-indole-2,3-dione, indoline-5,6-diol,    3,5-dimethoxypyridine-2,6-diamine, 6-methoxypyridine-2,3-diamine;    3,4-dihydro-2H-1,4-benzoxazin-6-amine; 4-hydroxy-N-methylindole,    1H-5-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one,    2,6-dimethylpyrazolo [1,5-b]-1,2,4-triazole, 2,6-dimethyl    [3,2-c]-1,2,4-triazole, 6-methylpyrazolo-[1,5-a]benzimidazole,    2,6-dihydroxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine,    5-methylpyrazolo[5,1-e]-1,2,3-triazole, 5-methyl-6-chloropyrazolo[5,    1-e]-1,2,3,-triazole, 5-phenylpyrazolo[5,1-e]-1,2,3-triazole and its    addition salts, 1H-2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole    tosylate, 7,8-dicyano-4-methylimidazolo-[3,2-a]imidazole,    2,7-dimethylpyrazolo[1,5-a]pyrimidin-5-one,    2,5-dimethylpyrazolo[1,5-a]pyrimidin-7-one, and    2-methyl-5-methoxymethyl-pyrazolo[1,5-a]pyrimidin-7-one;    6-Hydroxybenzomorpholine; and    3-Amino-2-methylamino-6-methoxypyridine;    1-Phenyl-3-methyl-5-pyrazolone-2,4-dihydro-5,2-phenyl-3H-pyrazole-3-one.

Preferred couplers include but are not limited to: phenol, resorcinol,and naphthol derivatives such as: naphthalene-1,7-diol,benzene-1,3-diol, 4-chlorobenzene-1,3-diol, naphthalen-1-ol,2-methyl-naphthalen-1-ol, naphthalene-1,5-diol, naphthalene-2,7-diol,benzene-1,4-diol, 2-methyl-benzene-1,3-diol, and2-isopropyl-5-methylphenol; 1,2,4-Trihydroxybenzene;1-Acetoxy-2-methylnaphthalene; and mixtures thereof;

-   m-phenylenediamine derivatives such as: benzene-1,3-diamine,    2-(2,4-diamino-phenoxy)-ethanol,    4-{3-[(2,4-diaminophenyl)oxy]propoxy}benzene-1,3-diamine,    2-(3-amino-4-methoxy-phenylamino)-ethanol,    2-[2,4-diamino-5-(2-hydroxy-ethoxy)-phenoxy]-ethanol, and    3-(2,4-diamino-phenoxy)-propan-1-ol;    2,4-Diamino-5-(2′-hydroxyethyloxy)toluene;    N,N-Dimethyl-3-ureidoaniline;    2,4-Diamino-5-fluorotoluenesulfatehydrate;    1-methyl-2,6-bis(2-hydroxyethylamino)benzene; and mixtures thereof;-   m-aminophenol derivatives such as: 3-amino-phenol,    5-amino-2-methyl-phenol, 5-(2-hydroxy-ethylamino)-2-methyl-phenol,    and 3-amino-2-methyl-phenol;    1-Methyl-2-hydroxy-4-(2′-hydroxyethyl)aminobenzene;    1-Hydroxy-3-amino-2,4-dichlorobenzene;    1,3-Bis-(2,4-Diaminophenoxy)propane;    1-Hydroxy-2-methyl-5-amino-6-chlorobenzene;    5-Amino-4-chloro-2-methylphenol; and mixtures thereof; and-   heterocyclic derivatives such as:    3,4-dihydro-2H-1,4-benzoxazin-6-ol,    4-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one,    1,3-benzodioxol-5-ol, 1,3-benzodioxol-5-amine, 1H-indol-4-ol,    1H-indole-5,6-diol, 1H-indol-7-ol, 1H-indol-5-ol, 1H-indol-6-ol,    1H-indole-2,3-dione, pyridine-2,6-diamine, 2-aminopyridin-3-ol,    4-hydroxy-N-methylindole, 1H-5-methylpyrazol-5-one,    1-phenyl-3-methylpyrazol-5-one,    2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole,    2,6-dimethyl[3,2-c]-1,2,4-triazole,    6-methylpyrazolo-[1,5-a]benzimidazole; 2,6-dihydroxypyridine;    2,6-dihydroxy-3,4-dimethylpyridine; 6-Hydroxybenzomorpholine;    2,6-Dihydroxy-3,4-dimethylpyridine;    3,5-Diamino-2,6-dimethoxypyridine;    3-Amino-2-methylamino-6-methoxypyridine;    1-Phenyl-3-methyl-5-pyrazolone-2,4-dihydro-5,2-phenyl-3H-pyrazole-3-one;    and mixtures thereof.

More preferred couplers include: benzene-1,3-diol;4-chlorobenzene-1,3-diol; 2-methyl-benzene-1,3-diol;benzene-1,3-diamine; 3-amino-phenol; 5-amino-2-methyl-phenol;1-Methyl-2-hydroxy-4-(2′-hydroxyethyl)aminobenzene;4-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one; 2-aminopyridin-3-ol;1-phenyl-3-methylpyrazol-5-one;1Phenyl-3-methyl-5-pyrazolone-2,4-dihydro-5,2-phenyl-3H-pyrazole-3-one;and mixtures thereof.

Primary Intermediate-Coupler Combinations

Preferred primary intermediate and coupler combinations include, but arenot limited to: (a) resorcinol, 4-amino-m-cresol, 2-methylresorcinol,4-amino-2-hydroxytoluene, m-aminophenol and 2-amino-4-hydroxyethylanisole sulphate; (b) resorcinol, 4-Amino-m-cresol, 2-methyl-resorcinol,4-amino-2-hydroxytoluene, m-aminophenol, 2-amino-4-hydroxyethyl anisolesulphate, 1-napthol and toluene-2,5-diamine; (c)2-methyl-5-hydroxyethylaminophenol, resorcinol, toluene-2,5-diamine,m-aminophenol, p-aminophenol and p-methylaminophenol; (d)2-methyl-5-hydroxyethylaminophenol, m-aminophenol, p-aminophenol,p-methylaminophenol and p-phenylenediamine; (e)1-hydroxyethyl-4,5-diamino pyrazole sulphate and m-aminophenol; and (f)2-methylresorcinol, p-aminophenol, 4-amino-2-hydroxytoluene,p-phenylenediamine and N,N-Bis(2-hydroxyethyl)-p-phenylenediamine.

Direct Dyes

The inventive compositions may also comprise compatible direct dyes, inan amount sufficient to provide additional coloursing, particularly withregard to intensity. Typically, such an amount will range from 0.05% to4%, by weight, of the composition. Suitable direct dyes include but arenot limited to: Acid Yellow 1, Acid Orange 3, Disperse Red 17, BasicBrown 17, Acid Black 52, Acid Black 1, Disperse Violet 4,4-Nitro-o-Phenylenediamine, 2-Nitro-p-Phenylenediamine, Picramic Acid,HC Red No. 13, 1,4-Bis-(2′-Hydroxyethyl)-amino-2-nitrobenzene, HC YellowNo. 5, HC Red No. 7, HC Blue No. 2, HC Yellow No. 4, HC Yellow No. 2, HCOrange No. 1, HC Red No. 1,2-Chloro-5-nitro-N-Hydroxyethyl-p-phenylenediamine, HC Red No.3,4-Amino-3-nitrophenol, 2-Hydroxyethylamino-5-nitroanisole,3-nitro-p-Hydroxyethylaminophenol, 2-amino-3-nitrophenol,6-nitro-o-toluidine, 3-methylamino-4-nitrophenoxyethanol,2-nitro-5-glycerymethylanaline, HC Yellow No. 11, HC Violet No. 1, HCOrange No. 2, HC Orange No. 3, HC Yellow No. 9,4-NitrophenylAminoethylurea, HC Red No. 10, HC Red No. 11, 2-Hydroxyethyl picramicacid, HC Blue No. 12, HC Yellow No. 6, Hydroxyethyl-2-nitro-p-toluidine,HC Yellow No. 12, HC Blue No. 10, HC Yellow No. 7, HC Yellow No. 10, HCBlue No. 9, N-ethyl-3-nitro PABA,4-amino-2-nitrophenyl-amine-2′-carboxylic acid,2-chloro-6-ethylamino-4-nitrophenol, 6-Nitro-2,5-pyridinediamine, HCViolet No. 2,2-amino-6-chloro-4-nitrophenol,4-hydroxypropylamino-3-nitrophenol, HC Yellow No. 13,1,2,3,4-Tetrahydro-6-nitrochinoxalin, HC Red No. 14, HC Yellow No. 15,HC Yellow No. 14, 3-Amino-6-methylamino-2-nitropyridine,2,6-diamino-3-((pyridine-3-yl)azo)pyridine, Basic Red No. 118, BasicOrange No. 69, N-(2-nitro-4-aminophenyl)-allylamine,4-[(4-Amino-3-methylphenyl)(4-Imino-3-methyl-2,5-Cyclohexadien-1-ylidene)Methyl]-2-Methyl-benzeneamine-Hydrochloride,1H-Imidazolium,2-[[4-(dimethyl-amino)phenyl]azo]-1,3-dimethylchloride,Pyridinium, 1-methyl-4-[(methylphenyl-hydrazono)methyl]-, methylsulfate, 1H-Imidazolium, 2-[(4-aminophenyl)azo]-1,3-dimethyl, chloride,Basic Red 22, Basic Red 76, Basic Brown 16, Basic Yellow 57,7-(2′,4′-Dimethyl-5′-sulfophenylazo)-5-sulfo-8-hydroxynaphthalene, AcidOrange 7, Acid Red 33,1-(3′-Nitro-5′-sulfo-6′-oxophenylazo)-oxo-naphthalene chromium complex,Acid Yellow 23, Acid Blue 9, Basic Violet 14, Basic Blue 7, Basic Blue26, Sodium salt of mixture of mono- & disulfonic acids (mainly thelatter) of quinophthlanone or 2-quinolylindandione, Basic Red 2, BasicBlue 99, Disperse Red 15, Acid Violet 43, Disperse Violet 1, Acid Blue62, Pigment Blue 15, Acid Black 132, Basic Yellow 29, Disperse Black 9,1-(N-Methylmorpholinium-propylamino)-4-hydroxy-anthraquinonemethylsulfate, HC Blue No. 8, HC Red No. 8, HC Green No. 1, HC Red No.9,2-Hydroxy-1,4-naphthoquinone, Acid Blue 199, Acid Blue 25, Acid Red 4,Henna Red, Indigo, Cochenille, HC Blue 14, Disperse Blue 23, DisperseBlue 3, Violet 2, Disperse Blue 377, Basic Red 51, Basic Orange 31,Basic Yellow 87, and mixtures thereof. Preferred direct dyes include butare not limited to: Disperse Black 9, HC Yellow 2, HC Yellow 4, HCYellow 15, 4-nitro-o-phenylenediamine, 2-amino-6-chloro-4-nitrophenol,HC Red 3, Disperse Violet 1, HC Blue 2, Disperse Blue 3, Disperse Blue377, Basic Red 51, Basic Orange 31, Basic Yellow 87, and mixturesthereof.

Oxidizing Agent

The developer compositions suitable for use with the inventivecompositions may comprise an oxidizing agent, present in an amountsufficient to bleach melanin pigment in hair and/or cause formation ofdye chromophores from oxidative dye precursors (including primaryintermediates and/or couplers when present). Typically, such an amountranges from 1% to 20%, preferably from 3% to 15%, more preferably from6% to 12%, by weight, of the developer composition. Inorganic peroxygenmaterials capable of yielding hydrogen peroxide in an aqueous medium arepreferred, and include but are not limited to: hydrogen peroxide;inorganic alkali metal peroxides (e.g. sodium periodate and sodiumperoxide); organic peroxides (e.g. urea peroxide, melamine peroxide);inorganic perhydrate salt bleaching compounds (e.g. alkali metal saltsof perborates, percarbonates, perphosphates, persilicates, andpersulphates, preferably sodium salts thereof), which may beincorporated as monohydrates, tetrahydrates, etc.; alkali metalbromates; enzymes; and mixtures thereof. Preferred is hydrogen peroxide.

Thickeners

The inventive compositions may comprise a thickener in an amountsufficient to provide the composition with a viscosity so that it can bereadily applied to the hair without unduly dripping off the hair andcausing mess. Typically, such an amount will be at least 0.1%,preferably at least 0.5%, more preferably, at least 1%, by weight, ofthe hair dyeing and/or developer composition.

Preferred for use herein are salt tolerant thickeners, including but notlimited to: xanthan, guar, hydroxypropyl guar, scleroglucan, methylcellulose, ethyl cellulose (available as AQUACOTE (TM)), hydroxyethylcellulose (NATROSOL (TM)), carboxymethyl cellulose, hydroxypropylmethylcellulose, microcrystalline cellulose, hydroxybutylmethyl cellulose,hydroxypropyl cellulose (available as KLUCEL (TM)), hydroxyethyl ethylcellulose, cetyl hydroxyethyl cellulose (available as NATROSOL (TM) Plus330), N-vinylpyrollidone (available as POVIDONE (TM)),Acrylates/Ceteth-20 Itaconate Copolymer (available as STRUCTURE (TM)3001), hydroxypropyl starch phosphate (available as STRUCTURE (TM) ZEA),polyethoxylated urethanes or polycarbamyl polyglycol ester (e.g.PEG-150/Decyl/SMDI copolymer (available as ACULYN(TM) 44),PEG-150/Stearyl/SMDI copolymer available as ACULYN(TM) 46),trihydroxystearin (available as THIXCIN(TM)), acrylates copolymer (e.g.available as ACULYN(TM) 33) or hydrophobically modified acrylatecopolymers (e.g. Acrylates/Steareth-20 Methacrylate Copolymer (availableas ACULYN(TM) 22), non-ionic amphophilic polymers comprising at leastone fatty chain and at least one hydrophilic unit selected frompolyether urethanes comprising at least one fatty chain, and blends ofCeteth-10 phosphate, Di-cetyl phosphate and Cetearyl alcohol (availableas CRODAFOS(TM) CES).

Chelants

The inventive compositions may comprise chelants in an amount sufficientto reduce the amount of metals available to interact with formulationcomponents, particularly oxidizing agents, more particularly peroxides.Typically such an amount will range from at least 0.25%, preferably atleast 0.5%, by weight, of the composition. Suitable chelants for useherein include but are not limited to: diamine-N,N′-dipolyacid,monoamine monoamide-N,N′-dipolyacid, andN,N′-bis(2-hydroxybenzyl)ethylenediamine-N,N′-diacetic acid chelants(preferably EDDS (ethylenediaminedisuccinic acid)), carboxylic acids(preferably aminocarboxylic acids), phosphonic acids (preferablyaminophosphonic acids) and polyphosphoric acids (in particular straightpolyphosphoric acids), their salts and derivatives.

pH Modifiers and Buffering Agents

The inventive compositions may further comprise a pH modifier and/orbuffering agent in an amount that is sufficiently effective to adjustthe pH of the composition to fall within a range from 3 to 13,preferably from 8 to 12, more preferably from 9 to 11. Suitable pHmodifiers and/or buffering agents for use herein include, but are notlimited to: ammonia, alkanolamides such as monoethanolamine,diethanolamine, triethanolamine, monopropanolamine, dipropanolamine,tripropanolamine, tripropanolamine, 2-amino-2-methyl-1-propanol, and2-amino-2-hydroxymethyl-1,3,-propandiol and guanidium salts, alkalimetal and ammonium hydroxides and carbonates, preferably sodiumhydroxide and ammonium carbonate, and acidulents such as inorganic andinorganic acids, e.g., phosphoric acid, acetic acid, ascorbic acid,citric acid or tartaric acid, hydrochloric acid, and mixtures thereof.

Carbonate Ion Source and Radical Scavenger System

The inventive compositions may further comprise a system comprising thecombination of at least one source of peroxymonocarbonate ions,preferably formed insitu from a source of hydrogen peroxide and acarbonate ion source, at least one source of alkalizing agents and atleast one source of radical scavenger, (as defined hereinafter), in anamount to sufficiently reduce odour and the damage to the hair fibres.Typically, such an amount will range from 0.1% to 15%, preferably 0.1%to 10%, more preferably 1% to 8%, by weight of the hair dyeingcomposition and/or the hair dyeing product composition, of the carbonateion, and from 0.1% to 10%, preferably from 1% to 7%, by weight of thecomposition, of radical scavenger and from 0.1 to 10%, preferably from0.5 to 5% of the alkalising agent. Preferably, the radical scavenger ispresent at an amount such that the ratio of radical scavenger tocarbonate ion is from 1:1 to 1:4. The radical scavenger is preferablyselected such that it is not an identical species as the alkalizingagent.

According to the present invention the compositions thus may alsocomprise at least a source of carbonate ions or carbamate ions orhydrocarbonate ions or any mixture thereof. Any source of these ions maybe utilized. Suitable sources for use herein include sodium, potassium,guanidine, arginine, lithium, calcium, magnesium, barium, ammonium saltsof carbonate, carbamate and hydrocarbonate ions and mixtures thereofsuch as sodium carbonate, sodium hydrogen carbonate, potassiumcarbonate, potassium hydrogen carbonate, guanidine carbonate, guanidinehydrogen carbonate, lithium carbonate, calcium carbonate, magnesiumcarbonate, barium carbonate, ammonium carbonate, ammonium hydrogencarbonate and mixtures thereof. Percarbonate salts may also be utilizedto provide both the source of carbonate ions and oxidizing agent.Preferred sources of carbonate ions, carbamate and hydrocarbonate ionsare sodium hydrogen carbonate, potassium hydrogen carbonate, ammoniumcarbamate and mixtures thereof.

According to the present invention the composition may also thuscomprise at least one source of alkalizing agent, preferably a source ofammonium ions and or ammonia. Any agent known in the art may be usedsuch as alkanolamides for example monoethanolamine, diethanolamine,triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine,2-amino-2-methyl-1,3-propanediol, 2-amino-2-methyl-1-propanol, and2-amino-2-hydroxymethyl-1,3-propanediol and guanidium salts.Particularly, preferred alkalizing agents are those which provide asource of ammonium ions. Any source of ammonium ions is suitable for useherein. Preferred sources include ammonium chloride, ammonium sulphate,ammonium nitrate, ammonium phosphate, ammonium acetate, ammoniumcarbonate, ammonium hydrogen carbonate, ammonium carbamate, ammoniumhydroxide, percarbonate salts, ammonia and mixtures thereof.Particularly preferred are ammonium carbonate, ammonium carbamate,ammonia and mixtures thereof.

The radical scavenger is a species that can react with a carbonateradical to convert the carbonate radical by a series of fast reactionsto a less reactive species. Suitable radical scavengers for use hereininclude compounds according to the general formula:R¹-Y—C(H)(R³)—R⁴—(C(H)(R⁵)—Y—R⁶)_(n)  (I):wherein Y is NR², O, or S, preferably NR², n is 0 to 2, and wherein R⁴is monovalent or divalent and is selected from: (a) substituted orunsubstituted, straight or branched, alkyl, mono- or poly-unsaturatedalkyl, heteroalkyl, aliphatic, heteroaliphatic, or heteroolefinicsystems, (b) substituted or unsubstituted, mono- or poly-cyclicaliphatic, aryl, or heterocyclic systems, or (c) substituted orunsubstituted, mono-, poly-, or per-fluoro alkyl systems; the systems of(a), (b) and (c) comprising from 1 to 12 carbon atoms and 0 to 5heteroatoms selected from O, S, N, P, and Si; and wherein R⁴ can beconnected to R³ or R⁵ to create a 5, 6 or 7 membered ring; and whereinR¹, R², R³, R⁵, and R⁶ are monovalent and are selected independentlyfrom: (a), (b) and (c) described herein above, or H.

Preferably, R⁴ is selected from: (a) substituted or unsubstituted,straight or branched, alkyl, heteroalkyl, aliphatic, heteroaliphatic, orheteroolefinic systems, (b) substituted or unsubstituted, mono- orpoly-cyclic aliphatic, aryl, or heterocyclic systems, or (c) substitutedor unsubstituted, mono-, poly-, or per-fluoro alkyl systems; morepreferably R⁴ is selected from (a) substituted or unsubstituted,straight or branched, alkyl, heteroalkyl, aliphatic, or heteroaliphaticsystems, (b) substituted or unsubstituted, aryl, or heterocyclicsystems, or (c) substituted or unsubstituted, mono-, poly-, orper-fluoro alkyl systems; more preferably substituted or unsubstituted,straight or branched, alkyl, or heteroalkyl systems.

Preferably, the R⁴ systems of (a), (b), and (c), described herein above,comprise from 1 to 8 carbon atoms, preferably from 1 to 6, morepreferably from 1 to 4 carbon atoms and from 0 to 3 heteroatoms;preferably from 0 to 2 heteroatoms; most preferably from 0 to 1heteroatoms. Where the systems contain heteroatoms, preferably theycontain 1 heteroatom. Preferred heteroatoms include O, S, and N; morepreferred are O, and N; and most preferred is 0.

Preferably, R¹, R², R³, R⁵, and R⁶ are selected independently from anyof the systems defined for R⁴ above, and H.

In alternative embodiments, any of R¹, R², R³, R⁴, R⁵, and R⁶ groups aresubstituted. Preferably, the substituent(s) is selected from: (a) thegroup of C-linked monovalent substituents consisting of: (i) substitutedor unsubstituted, straight or branched, alkyl, mono- or poly-unsaturatedalkyl, heteroalkyl, aliphatic, heteroaliphatic, or heteroolefinicsystems, (ii) substituted or unsubstituted, mono- or poly-cyclicaliphatic, aryl, or heterocyclic systems, or (iii) substituted orunsubstituted, mono-, poly-, or per-fluoro alkyl systems; said systemsof (i), (ii) and (iii) comprising from 1 to 10 carbon atoms and 0 to 5heteroatoms selected from O, S, N, P, and Si; (b) the group of S-linkedmonovalent substituents consisting of SA¹, SCN, SO₂A₁, SO₃A¹, SSA¹,SOA₁, SO₂NA¹A², SNA¹A², and SONA¹A²; (c) the group of O-linkedmonovalent substituents consisting of OA¹, OCN and ONA¹A²; (d) the groupof N-linked monovalent substituents consisting of NA¹A², (NA¹A²A³)⁺, NC,NA¹OA², NA¹SA², NCO, NCS, NO₂, N═NA¹, N═NOA¹, NA¹CN, NA¹NA²A³; (e) thegroup of monovalent substituents consisting of COOA¹, CON₃, CONA¹ ₂,CONA¹COA², C(═NA¹)NA¹A², CHO, CHS, CN, NC, and X; and (f) the groupconsisting fluoroalkyl monovalent substituents consisting of mono-,poly-, or per-fluoro alkyl systems comprising from 1 to 12 carbon atomsand 0 to 4 heteroatoms.

For the groups (b) to (e), described above, A¹, A², and A³ aremonovalent and are independently selected from: (1) H, (2) substitutedor unsubstituted, straight or branched, alkyl, mono- or poly-unsaturatedalkyl, heteroalkyl, aliphatic, heteroaliphatic, or heteroolefinicsystems, (3) substituted or unsubstituted, mono- or poly-cyclicaliphatic, aryl, or heterocyclic systems, or (4) substituted orunsubstituted, mono-, poly-, or per-fluoro alkyl systems; said systemsof (2), (3) and (4) comprising from 1 to 10 carbon atoms and 0 to Sheteroatoms selected from O, S, N, P, and Si; and wherein X is a halogenselected from the group consisting of F, Cl, Br, and I.

Preferred radical scavengers according to the present invention areselected from the classes of alkanolamines, amino sugars, amino acids,esters of amino acids and mixtures thereof. Particularly preferredcompounds are: monoethanolamine, 3-amino-1-propanol, 4-amino-1-butanol,5-amino-1-pentanol, 1-amino-2-propanol, 1-amino-2-butanol,1-amino-2-pentanol, 1-amino-3-pentanol, 1-amino-4-pentanol,3-amino-2-methylpropan-1-ol, 1-amino-2-methylpropan-2-ol,3-aminopropane-1,2-diol, glucosamine, N-acetylglucosamine, glycine,arginine, lysine, proline, glutamine, histidine, sarcosine, serine,glutamic acid, tryptophan, and mixtures thereof, and the salts such asthe potassium, sodium and ammonium salts thereof and mixtures thereof.

Especially preferred compounds are glycine, sarcosine, lysine, serine, 2methoxyethylamine, glucosamine, glutamic acid, morpholine, piperdine,ethylamine, 3 amino-1-propanol and mixtures thereof.

Conditioning Agents

The compositions of the present invention may comprise or are used incombination with a composition comprising a conditioning agent.Conditioning agents suitable for use herein are selected from siliconematerials, amino silicones, fatty alcohols, polymeric resins, polyolcarboxylic acid esters, cationic polymers, cationic surfactants,insoluble oils and oil derived materials and mixtures thereof.Additional materials include mineral oils and other oils such asglycerin and sorbitol.

The conditioning agent will generally be used at levels of from about0.05% to about 20% by weight of the hair dyeing product composition,preferably of from about 0.1% to about 15%, more preferably of fromabout 0.2% to about 10%, even more preferably of from about 0.2% toabout 2%.

Particularly useful conditioning materials are cationic polymers.Conditioners of cationic polymer type may be chosen from those alreadyknown by those skilled in the art as improving at least one cosmeticproperties of keratin fibres treated with a cosmetic composition.Cationic polymers can be chosen from those comprising units of at leastone amine group chosen from primary, secondary, tertiary and quaternaryamine groups that may either form part of the main polymer chain, or beborne by a side substituent that is directly attached to the mainpolymer chain. Such cationic polymers generally have a number averagemolecular mass ranging from 500 to 5×10⁶, or more preferably from 1000to 3×10⁶.

II. Methods of Manufacture

The compounds of this invention may be obtained using conventionalmethods. A general description of how to make the compounds is providedabove and specific examples are provided below. The compositions of thisinvention may also be obtained using conventional methods. The hairdyeing compositions may be formed as solutions, preferably as aqueous oraqueous-alcohol solutions. The hair dye product compositions maypreferably be formed as thick liquids, creams, gels, or emulsions whosecomposition is a mixture of the dye compound and other dye ingredientswith conventional cosmetic additive ingredients suitable for theparticular preparation and preferably with the developer composition.

III. Methods of Use

The inventive hair dyeing compositions may be used by admixing them witha suitable oxidant, which reacts with the oxidative dye precursors todevelop the hair dye product composition. The oxidant is usuallyprovided in an aqueous composition, i.e. developer composition, whichnormally is provided as a separate component of the finished hair dyeingproduct system and present in a separate container. The developercomposition may also contain, to the extent compatible, variousingredients needed to form the developer composition, e.g. peroxidestabilizers, foam formers, etc., and may incorporate one or more of theadjuvants referred to above. Upon mixing the hair dyeing composition andthe developer composition to form a hair dye product composition, theadjuvants are provided in the hair dye product composition as it isapplied to the hair to achieve desired product attributes, e.g., pH,viscosity, rheology, etc.

The hair dyeing product composition as it is applied to the hair, can beweakly acidic, neutral or alkaline according to their composition,typically having a pH from 6 to 11, preferably from 7 to 10, morepreferably from 8 to 10. The pH of the developer composition istypically acidic, and generally the pH is from 2.5 to 6.5, preferablyfrom 3 to 5. The pH of the hair dye and developer compositions may beadjusted using a pH modifier as mentioned above.

In order to use the hair dyeing product composition, the above-describedcompositions are mixed immediately prior to use and a sufficient amountof the mixture is applied to the hair, according to the hair abundance,generally from 60 to 200 grams. Upon such preparation the hair dyeproduct composition is applied to the hair to be dyed and remains incontact with the hair for an amount of time effective to dye the hair.Typically, the hair dye product composition is allowed to act on thehair for 2 to 60, preferably 15 to 45, more preferably, 30 minutes, at atemperature ranging from 15□ to 50° C. Thereafter, the hair is rinsedwith water, to remove the hair dye product composition and dried. Ifnecessary, the hair is washed with a shampoo and rinsed, e.g., withwater or a weakly acidic solution, such as a citric acid or tartaricacid solution, and dried. Optionally, a separate conditioning productmay also be provided.

Together, the hair dyeing composition and the developer composition forma system for dyeing hair. This system may be provided as a kitcomprising in a single package separate containers of the hair dyeingcomposition, the developer composition, the optional conditioner orother hair treatment product, and instructions for use.

EXAMPLES Example 1 Synthesis of 2-amino-3,5,diimethyl phenol

Step 1: 4-Chloro-3,5-dimethyl-2-nitrophenol

4-Chloro-3,5-dimethyl-phenol (20.0 g, 128 mmol) was dissolved in glacialacid (150 ml) and the solution was cooled to 5° C. Then nitric acid 65%(12.4 g, 128 mmol) was added dropwise while temperature was kept below20° C. by external cooling. After the addition was complete stirring wascontinued for 1 hour at ambient temperature. The reaction mixture waspoured into ice/water (1:1, 500 g) whereupon an orange solidprecipitated. The solid was filtered off, washed with water and dried.Yield: 23.2 g (90.1%). ¹H-NMR (DMSO-d₆): δ=11.0 (s, 1H); 6.9 (s, 1H);2.3 (s, 3H); 2.2 ppm (s, 3H).

Step 2: 2-Amino-3,5-dimethyl-phenol hydrochloride

4-Chloro-3,5-dimethyl-2-nitrophenol (21.0 g, 105 mmol) was suspended in200 ml water and 50 ml 2N sodium hydroxide. Then Pd/C 10% (2 g) wasadded and the mixture was hydrogenated at 9 bar/ambient temperatureovernight. The catalyst was then filtered off and the clear solution wasneutralized with 2N hydrochloric acid. The product was extracted with200 ml ethyl acetate, three times each. After separating and drying theorganic layer was concentrated under reduced pressure. Then 3Mhydrochloric acid was added (50 ml) and the product crystallized out.After cooling in an ice bath the product was filtered off, washed withethyl acetate and dried. Yield: 10.6 g (58%) of a pale yellowish solid.¹H-NMR (DMSO-d₆): δ=10.6 (s, 1H); 9.5 (s broad, 3H); 6.7 (s, 1H); 6.6(s, 1H); 2.3 (s, 3H); 2.2 ppm(s, 3H).

Elemental Analysis, C₈H₁₁NO.HCl (M=173.64) % C % H % N Calculated 55.346.97 8.07 Found 55.30 7.18 7.8

TABLE 1 Examples 1 to 10, which illustrate the inventive hair dyeingcompositions, may be formulated as thickened, aqueous solutions, byconventional methods. A suitable procedure is described below.Composition Example Number Ingredient 1 2 3 4 5 6 7 8 9 10 SodiumSulphite — — 0.1 0.1 0.1 0.1 0.1 0.3 0.1 — Ascorbic Acid 0.5 0.1 — 0.10.3 — 0.6 0.1 0.1 0.2 Ammonium Hydroxide 6   8   8   7   8   9   10  8   8   10   Ethylenediamedisuccinic acid — — — 1   — 1   — 0.5 — 1.5Oleth 5 1   2   3   0.5 1   1.5 — 0.8 2   1   Oleth 2 0.8 — 0.8 0.8 1.52   0.8 0.5 0.8 2.5 Oleic Acid 0.9 1   — 0.3 — 0.9 0.9 0.8 1.1 0.9Soytrimonium chloride 7   6   6   7   7   — — 8   5   7   Cocamide DEA3   1   1   3   0.5 0.8 — — 3   2   EDTA (Na₄ salt) 0.1 0.1 0.1 0.1 0.1— 0.1 0.1 0.1 0.1 1,4 diaminobenzene 0.8 0.5 — 0.5 0.8 — 0.5 0.6 0.5 0.84-aminophenol 0.2 — — 0.1 0.2 — — 0.2 0.1 0.2 3-aminophenol 0.5 0.5 —0.6 1   — 0.5 1   0.6 1   4-amino-3-methylphenol 0.2 — — 0.2 0.2 — 1  0.2 0.3 2-(4,5-diamino-1H- — 0.5 — — 0.5 — 0.5 1   — 0.3pyrazol-1-yl)ethanol N,N-Bis(2-hydroxyethyl)- — 0.4 — 1   0.2 — 0.2 —0.2 0.3 p-phenylenediamine 2-aminophenol 1   1   — — — — — — — —3,5-dimethyl-2- — — — 1   — — — — — — aminophenol 3,5-dimethoxymethyl2-aminophenol 1   0.5 — — 1   1.5 1   — — — 3,5-diethyl 2-aminophenol —— 1   0.8 — — — 1   1   1   Propylene Glycol 8.2 8   7.8 8.2 8.4 8   8.28.2 7.8 8.2 Hexylene Glycol 8   7   8   6   8   8   — 9   8   9   EthoxyDiglycol 4.2 4   4.6 4.2 4.2 5   4.2 3   4.2 4.2 Water qs qs qs qs qs qsqs qs qs qs

To prepare pre-mix: Add to a suitable vessel in the following order,citric acid, ethoxy diglycol, oleic acid, propylene glycol, andcocaamidopropyl betaine, then agitate until fully dispersed, then addOleth-10, Oleth-2 and acrylate co-polymers, continue the agitation for10 minutes and transfer to main vessel. To the main vessel then addwater (heated to 50° C.), oleic acid, water, sodium sulphite, and EDTA.Next weigh out and add the ascorbic acid, then stir well untildissolved. Separately weigh dyes into a clean beaker and transfer alsoto the main vessel. Add the dyes and stir until dissolved (heat to 40°C. as necessary). Cool to room temperature with stirring, add theammonium hydroxide and water with stirring, add citric acid to pH 10,and transfer to the storage container. TABLE 2 Examples 11 to 20, whichillustrate the inventive hair dyeing compositions, may be formulated asemulsions, by conventional methods. The procedure described for Examples3 to 12 is suitable. Composition Example Number Ingredient 11 12 13 1415 16 17 18 19 20 Sodium Sulphite — — 0.1 0.1 0.1 0.1 0.1 0.3 0.1 —Ascorbic Acid 0.5 0.1 — 0.1 0.3 — 0.6 0.1 0.1 0.2 Ammonium Carbonate 3  6   2   — 4   8   2   — 4   6   Potassium Hydrogen — — 1.5 2   — — 2  2   — — Carbonate Ammonium Acetate — — — 2   — — — 2   — — Ceteareth 251   — 1.5 1   1   2   1   1   — 1   Cetyl Alcohol 1.6 1.2 1.6 1.6 — 1.81.6 1.6 2   1.6 Stearyl Alcohol 3.3 — 3.3 3   3.3 2.5 3.3 4   3.3 —Sodium Benzoate 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Phenoxyethanol0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 EDTA (Na₄ salt) 0.1 0.1 0.1 0.10.1 0.1 0.1 0.1 0.1 0.1 Sodium Glycinate 2   5   3   1   — — — — — 3  Glutamic Acid — — — 2   2   6   2   — — — Glucosamine — — — — — — 2  4   4   3   1,4 diaminobenzene 0.8 0.5 0.6 — 0.8 0.8 0.5 0.6 — 0.84-aminophenol 0.2 0.3 0.2 — 0.2 0.2 0.3 0.2 — 0.2 3-aminophenol 1   0.51   — 1   1   0.5 1   — 1   1,3 dihydroxybenzene 1.6 1.2 1.6 — 1.6 1.61.2 1.6 — 1.6 4-amino-3-methylphenol 0.2 — — 0.2 0.2 — 1   0.2 0.32-(4,5-diamino-1H- — 0.5 — — 0.5 — 0.5 1   — 0.3 pyrazol-1-yl)ethanolN,N-Bis(2- — 0.4 — 1   0.2 — 0.2 — 0.2 0.3 hydroxyethyl)-p-phenylenediamine 2-aminophenol 1   1   — — — — — — — — 3,5-dimethyl-2- —— 1   — — — — — — — aminophenol 3,5-dimethoxymethyl 2- 1   1   1   1  1   1   1   — — — aminophenol 3,5-diethyl — 1   1   — — — — 1   1   1  2-aminophenol pH adjust to pH 9.0 qs qs qs qs qs qs qs qs qs qs Water qsqs qs qs qs qs qs qs qs qs

TABLE 3 Examples 21 to 30, which illustrate the inventive hair dyeingcompositions, may be formulated as emulsions, by conventional methods.The procedure described for Examples 3 to 12 is suitable. CompositionExample Number Ingredient 21 22 23 24 25 26 27 28 29 30 Sodium Sulphite— — 0.1 0.1 0.1 0.1 0.1 0.3 0.1 — Ascorbic Acid 0.5 0.1 — 0.1 0.3 — 0.60.1 0.1 0.2 Ammonium Carbonate 3   6   2   — 4   8   2   — 4   6  Potassium Hydrogen — — 1.5 2   — — 2   2   — — Carbonate AmmoniumAcetate — — — 2   — — — 2   — — Blended phosphate 3   2   1.5 4   3  1   1.8 2   3   3   thickener¹ EDTA (Na₄ salt) 0.1 0.1 0.1 0.1 0.1 0.10.1 0.1 0.1 0.1 Sodium Glycinate 2   5   3   1   — — — — — 3   GlutamicAcid — — — 2   2   6   2   — — — Glucosamine — — — — — — 2   4   4   3  1,4 diaminobenzene 0.8 — 0.6 0.5 0.8 0.8 0.5 0.6 — 0.8 4-aminophenol 0.2— 0.2 0.1 0.2 0.2 0.3 0.2 — 0.2 3-aminophenol 1   — 1   0.6 1   1   0.51   — 1   1,3 dihydroxybenzene 1.6 — 1.6 0.8 1.6 1.6 1.2 1.6 — 1.64-amino-3-methylphenol 0.2 — — 0.2 0.2 — 1   0.2 0.3 2-(4,5-diamino-1H-— 0.5 — — 0.5 — 0.5 1   — 0.3 pyrazol-1- yl)ethanol N,N-Bis(2- — 0.4 —1   0.2 — 0.2 — 0.2 0.3 hydroxyethyl)-p- phenylenediamine 2-aminophenol1   — — — — — — — — — 3,5-dimethyl-2- — — 1   1   — — — — — —aminophenol 3,5-dimethoxymethyl 2- 1   1   — — 1   1   1   — — —aminophenol 3,5-diethyl — — 1   1   — — — 1   1   1   2-aminophenol pHadjust to pH 9.0 qs qs qs qs qs qs qs qs qs qs Water qs qs qs qs qs qsqs qs qs qs¹Ceteth-10 phosphate/di-cetyl phosphate/cetearyl alcohol blend,available as CRODAFOS (TM) CES, from Croda (United Kingdom).

TABLE 4 Example 31 illustrates developer compositions which may be usedwith the hair dyeing example formulations number 1-30 and may beformulated by conventional methods described below. Composition ExampleNumber 31 Ingredient % Weight Oleyl Alcohol 0.1-2.0 Steareth-21 1.0-5.0Acrylates Copolymer  1.0-10.0 PEG-50 0.1-2.0 Water 50.0-90.0 HydrogenPeroxide - 50% 10.0-15.0 Acrylates/Steareth-20 Methacrylate 0.1-2.0copolymer Oleth-2 0.1-2.0 Oleth-5 0.1-2.0 Etidronic Acid 0.01-0.1 Disodium EDTA 0.01-0.1  Simethicone 0.001-0.01 To prepare:—All vessels should first be passivated as follows: Fillvessel to about 10% full with concentrated hydrogen peroxide and thenfill to the top with deionized water (DI). Add plastic overhead stirrer,plastic spatulas and glass thermometer that will be used in process.Swirl to mix; pour solution out, rinse with DI water, fill with freshperoxide solution; add stirrer and spatulas. Cover with plasticfilm/cover; allow to stand for 24 hours, pour out and dry. Once done add60% water to a tared vessel, heat to 70-75° C. and maintain thistemperature. Add the steareth-21 and stir until dissolved. Whilststirring pre-melt the PEG-50 on a hot plate and when the steareth hasdissolved add to the batch. Then add each of the following ingredientsone at a time, waiting for each to dissolve before adding the next;Oleth-2, Oleth-5, Oleyl Alcohol, EDTA and Etidronic acid. Mix the batchfor 15 minutes. Remove from the heat and add the remaining water, thenallow the batch to cool to 35° C. Add the hydrogen peroxide, followed bythe remaining ingredients. Finally retare the vessel and q.s. withwater. Product can be stored in storage containers (no metal caps) forup to 6 months.

The exemplified hair dyeing compositions are typically pre-mixed in a1:1 ratio with the developer composition prior to application onto thekeratinous fibres.

The following performance data was generated by dyeing out 0.02Mconcentration of the dye precursor from the exemplified hair dyeingproduct compositions described hereinabove. The hair dyeing productcomposition was applied at a dosage of four grams of product per gram ofhair. The hair switch was then placed in an oven at 30° C. for 30minutes, after which time the hair switch was rinsed in warm tap wateruntil the resulting water ran clear and was then left to dry. Once dry,the colour of the switch was measured on a Minolta 1600DSpectrophotometer. The Lab values of this compound verses referencecompounds (2-amino phenol and 5-methyl 2-aminophenol) below clearlyillustrate that this compound provides at least equivalent performancewith regard to delivery of yellow colour. Compound (all 0.02M) L A b2-aminophenol 68.4 5.62 38.7 5-methyl 2-aminophenol 76.0 1.02 57.233,5-dimethyl 77.9 −9.3 53.4 2-aminophenol

All documents cited in the Detailed Description of the Invention are, inrelevant part, incorporated herein by reference; the citation of anydocument is not to be construed as an admission that it is prior artwith respect to the present invention. To the extent that any meaning ordefinition of a term in this written document conflicts with any meaningor definition of the term in a document incorporated by reference, themeaning or definition assigned to the term in this written documentshall govern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are the scope of this invention.

1. A composition for the oxidative dyeing of keratin fibres, comprisinga medium suitable for dyeing and from about 0.001% to about 10% byweight of the composition of a compound (I), or its salts with aninorganic or organic acid according to the formula:

wherein both of R³ and R⁵ are substituted and are independently selectedfrom: (a) the group of C-linked monovalent substituents consisting of:(i) substituted or unsubstituted, straight or branched, alkyl, mono- orpoly-unsaturated alkyl, heteroalkyl, aliphatic, heteroaliphatic, orheteroolefinic systems, (ii) substituted or unsubstituted, mono- orpoly-cyclic aliphatic, aryl, or heterocyclic systems, and (iii)substituted or unsubstituted, mono-, poly-, or per-fluoro alkyl systems;said systems of (i), (ii) and (iii) comprising from about 1 to about 10carbon atoms and 0 to 5 heteroatoms selected from O, S, N, P, and Si;(b) the group of S-linked monovalent substituents consisting of SA¹,SCN, SSA¹, SOA₁, SO₂NA¹A¹, SNAA 2, and SONA¹A²; (c) the group ofO-linked monovalent substituents consisting of OA⁴, OCN and ONA¹A¹; (d)the group of N-linked monovalent substituents consisting of NA⁵,(NA¹A²A³)⁺, NC, NA¹OA², NA¹SA², NCO, NCS, N═NA¹, N═NOA¹, NA¹CN, andNA¹NA¹A¹; (e) the group of monovalent substituents consisting of CON₃,CONA¹ ₂, CONA¹COA², C(═NA¹)NA¹A¹, CHO, CHS, CN, NC, and X; and (f) thegroup of fluoroalkyl monovalent substituents consisting of mono-, poly-,and per-fluoro alkyl systems comprising from about 1 to about 12 carbonatoms and about 0 to about 4 heteroatoms; and wherein for the groups (b)to (e), described herein above, A¹, A², and A³ are monovalent and areindependently selected from: (1) H, (2) substituted or unsubstituted,straight or branched, alkyl, mono- or poly-unsaturated alkyl,heteroalkyl, aliphatic, heteroaliphatic, or heteroolefinic systems, (3)substituted or unsubstituted, mono- or poly-cyclic aliphatic, aryl, orheterocyclic systems, or (4) substituted or unsubstituted, mono-, poly-,or per-fluoro alkyl systems; said systems of (2), (3) and (4) comprisingfrom about 1 to about 10 carbon atoms and about 0 to about 5 heteroatomsselected from O, S, N, P, and Si; and wherein X is a halogen selectedfrom the group consisting of F, Cl, Br, and I, A⁴ is monovalent and isindependently selected from: (1) substituted or unsubstituted, straightor branched, alkyl, mono- or poly-unsaturated alkyl, heteroalkyl,aliphatic, heteroaliphatic, or heteroolefinic systems, (2) substitutedor unsubstituted, mono- or poly-cyclic aliphatic, aryl, or heterocyclicsystems, or (3) substituted or unsubstituted, mono-, poly-, orper-fluoro alkyl systems; said systems of (1), (2) and (3) comprisingfrom about 2 to about 10 carbon atoms and about 0 to about 5 heteroatomsselected from O, S, N, P, and Si, A⁵ is monovalent and is independentlyselected from: (1) substituted or unsubstituted, straight or branched,alkyl, mono- or poly-unsaturated alkyl, heteroalkyl, aliphatic,heteroaliphatic, or heteroolefinic systems, (2) substituted orunsubstituted, mono- or poly-cyclic aliphatic, aryl, or heterocyclicsystems, or (3) substituted or unsubstituted, mono-, poly-, orper-fluoro alkyl systems; said systems of (1), (2) and (3) comprisingfrom about 1 to about 10 carbon atoms and about 0 to about 5 heteroatomsselected from O, S, N, P, and Si; and wherein X is a halogen selectedfrom the group consisting of F, Cl, Br, and I and wherein R² is selectedfrom H and any of the groups defined for R³ and R⁵.
 2. A compositionaccording to claim 1, wherein R³ and R⁵ are independently selected from:(a) the group of C-linked monovalent substituents consisting of: (i)substituted or unsubstituted, straight or branched, alkyl, mono- orpoly-unsaturated alkyl, heteroalkyl, aliphatic, heteroaliphatic, orheteroolefinic systems, (ii) substituted or unsubstituted, mono- orpoly-cyclic aliphatic, aryl, or heterocyclic systems, and (iii)substituted or unsubstituted, mono-, poly-, or per-fluoro alkyl systems;said systems of (i), (ii) and (iii) comprising from about 1 to about 10carbon atoms and about 0 to about 5 heteroatoms selected from O, S andN; (b) the group of monovalent substituents consisting of CON₃, CONA¹ ₂,CONA¹COA², C(═NA¹)NA¹A², CHO, CHS, CN, NC, and X; and (c) the group offluoroalkyl monovalent substituents consisting of mono-, poly-, orper-fluoro alkyl systems comprising from about 1 to about 8 carbon atomsand about 0 to about 3 heteroatoms.
 3. A composition according to claim1, wherein R³ and R⁵ are independently selected from the group ofC-linked monovalent substituents consisting of: (i) substituted orunsubstituted, straight or branched, alkyl, mono- or poly-unsaturatedalkyl, heteroalkyl, aliphatic, heteroaliphatic, or heteroolefinicsystems, (ii) substituted or unsubstituted, mono- or poly-cyclicaliphatic, aryl, or heterocyclic systems, and (iii) substituted orunsubstituted, mono-, poly-, or per-fluoro alkyl systems; said systemsof (i), (ii) and (iii) comprising from about 1 to about 6 carbon atomsand about 0 to about 2 heteroatoms selected from O, S and N.
 4. Acomposition according to claim 1, wherein R³ and R⁵ are independentlyselected from the group of C-linked monovalent substituents consistingof: substituted or unsubstituted, straight or branched, alkyl, mono- orpoly-unsaturated alkyl, heteroalkyl, aliphatic, heteroaliphatic, orheteroolefinic systems comprising from about 1 to about 6 carbon atomsand about 0 to about 2 heteroatoms selected from O, S and N and R is H.5. A composition according to claim 1, wherein R³ and R⁵ areindependently selected from methyl, ethyl and CH₂—O—CH₃, and R² is H. 6.A composition according to claim 1, further comprising a primaryintermediate selected from p-phenylenediamine, p-aminophenol,o-phenylenediamine, o-aminophenol, heterocyclics, derivatives thereof,and mixtures thereof.
 7. A composition according to claim 1, furthercomprising a coupler selected from phenol, resorcinol, naphthol,m-phenylenediamine, m-aminophenol, heterocyclics, derivatives thereof,and mixtures thereof.
 8. A composition according to claim 1, furthercomprising a primary intermediate and coupler combination selected fromthe group consisting of: (a) resorcinol, 4-amino-m-cresol,2-methylresorcinol, 4-amino-2-hydroxytoluene, m-aminophenol and2-amino-4-hydroxyethyl anisole sulphate; (b) resorcinol,4-amino-m-cresol, 2-methylresorcinol, 4-amino-2-hydroxytoluene,m-aminophenol, 2-amino-4-hydroxyethyl anisole sulphate, 1-napthol andtoluene-2,5-diamine; (c) 2-methyl-5-hydroxyethylaminophenol, resorcinol,toluene-2,5-diamine, m-aminophenol, p-aminophenol andp-methylaminophenol; (d) 2-methyl-5-hydroxyethylaminophenol,m-aminophenol, p-aminophenol, p-methylaminophenol andp-phenylenediamine; (e) 1-hydroxyethyl-4,5-diamino pyrazole sulphate andm-aminophenol; and (f) 2-methylresorcinol, p-aminophenol,4-amino-2-hydroxytoluene, p-phenylenediamine andN,N-Bis(2-hydroxyethyl)-p-phenylenediamine.
 9. A composition accordingto claim 1, further comprising an oxidizing agent selected from thegroup consisting of: hydrogen peroxide; inorganic alkali metalperoxides; organic peroxides; inorganic perhydrate salt bleachingcompounds; alkali metal bromates; enzymes; and mixtures thereof.
 10. Acomposition according to claim 1, further comprising a thickenerselected from the group consisting of: xanthan, guar, hydroxypropylguar, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose,N-vinylpyrollidone, Acrylates/Ceteth-20 Itaconate copolymer,PEG-150/Decyl/SMDI copolymer, PEG-150/Stearyl/SMDI copolymer,trihydroxystearin, Acrylates/Steareth-20 Methacrylate copolymer, blendedCeteth-10 phosphate/Di-cetyl phosphate/Cetearyl alcohol, and mixturesthereof.
 11. A composition according to claims 1 further comprising achelant.
 12. A composition according to claim 1, wherein said mediumcomprises a solvent selected from the group consisting of water,ethanol, propanol, isopropanol, glycerol, 1,2-propylene glycol, hexyleneglycol, ethoxy diglycol, and mixtures thereof.
 13. A method foroxidative dyeing of keratin fibres, said method comprising the step ofapplying a composition according to claim 1 to keratin fibres in thepresence of an oxidizing agent.
 14. A multi-compartment device for theoxidative dyeing of keratin fibres or a multi-compartment kit for theoxidative dyeing of keratin fibres, comprising at least a firstcompartment containing a composition according to claim 1, and at leasta second compartment containing an oxidizing composition.